CN106554433B - Spherical load type metallocene catalyst - Google Patents
Spherical load type metallocene catalyst Download PDFInfo
- Publication number
- CN106554433B CN106554433B CN201510627473.9A CN201510627473A CN106554433B CN 106554433 B CN106554433 B CN 106554433B CN 201510627473 A CN201510627473 A CN 201510627473A CN 106554433 B CN106554433 B CN 106554433B
- Authority
- CN
- China
- Prior art keywords
- zirconium
- spherical
- phosphoric acid
- titanium
- added
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000012968 metallocene catalyst Substances 0.000 title claims abstract description 112
- 239000003054 catalyst Substances 0.000 claims abstract description 73
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical group C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims abstract description 65
- 238000002360 preparation method Methods 0.000 claims abstract description 51
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 44
- 150000003755 zirconium compounds Chemical class 0.000 claims abstract description 42
- 150000001875 compounds Chemical class 0.000 claims abstract description 38
- 229920000642 polymer Polymers 0.000 claims abstract description 14
- 150000001336 alkenes Chemical class 0.000 claims abstract description 10
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 369
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 163
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 119
- 238000003756 stirring Methods 0.000 claims description 111
- 239000010936 titanium Substances 0.000 claims description 111
- 239000001257 hydrogen Substances 0.000 claims description 107
- 229910052739 hydrogen Inorganic materials 0.000 claims description 107
- 150000002431 hydrogen Chemical class 0.000 claims description 102
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 99
- 229910052719 titanium Inorganic materials 0.000 claims description 99
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 85
- -1 phosphoric acid hydrogen titanium/zirconium class Chemical class 0.000 claims description 36
- 230000004913 activation Effects 0.000 claims description 35
- 239000007787 solid Substances 0.000 claims description 34
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 21
- 229910052726 zirconium Inorganic materials 0.000 claims description 21
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical class Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 claims description 15
- 239000004411 aluminium Substances 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 12
- ZXDGBPHTBIQCLN-UHFFFAOYSA-N phenylphosphonic acid;titanium Chemical compound [Ti].OP(O)(=O)C1=CC=CC=C1 ZXDGBPHTBIQCLN-UHFFFAOYSA-N 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 11
- 238000006555 catalytic reaction Methods 0.000 claims description 11
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- 239000010703 silicon Substances 0.000 claims description 11
- 125000003963 dichloro group Chemical group Cl* 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 229910010068 TiCl2 Inorganic materials 0.000 claims description 8
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 8
- YMNSMABYXHSAGT-UHFFFAOYSA-N phenylphosphonic acid phosphoric acid Chemical compound OP(O)(O)=O.OP(O)(=O)c1ccccc1 YMNSMABYXHSAGT-UHFFFAOYSA-N 0.000 claims description 7
- 150000003016 phosphoric acids Chemical class 0.000 claims description 7
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- FAJJYXYRMUZENM-UHFFFAOYSA-L [Cl-].[Cl-].[Zr++]C1c2ccccc2-c2ccccc12 Chemical compound [Cl-].[Cl-].[Zr++]C1c2ccccc2-c2ccccc12 FAJJYXYRMUZENM-UHFFFAOYSA-L 0.000 claims description 5
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 239000002114 nanocomposite Substances 0.000 claims description 5
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 claims description 5
- 239000003426 co-catalyst Substances 0.000 claims description 4
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 4
- 239000013049 sediment Substances 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- ATYZRBBOXUWECY-UHFFFAOYSA-N zirconium;hydrate Chemical compound O.[Zr] ATYZRBBOXUWECY-UHFFFAOYSA-N 0.000 claims description 4
- JAKYKQHNJUDFCT-UHFFFAOYSA-N C1=CC=C2C([Zr])C=CC2=C1 Chemical compound C1=CC=C2C([Zr])C=CC2=C1 JAKYKQHNJUDFCT-UHFFFAOYSA-N 0.000 claims description 3
- DDDRMZMSFMQPPC-UHFFFAOYSA-L [Cl-].[Cl-].C1C=CC=C2C([Zr+2])CCC21 Chemical class [Cl-].[Cl-].C1C=CC=C2C([Zr+2])CCC21 DDDRMZMSFMQPPC-UHFFFAOYSA-L 0.000 claims description 3
- KUNZSLJMPCDOGI-UHFFFAOYSA-L [Cl-].[Cl-].[Hf+2] Chemical class [Cl-].[Cl-].[Hf+2] KUNZSLJMPCDOGI-UHFFFAOYSA-L 0.000 claims description 3
- 238000005660 chlorination reaction Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 229910052735 hafnium Inorganic materials 0.000 claims description 3
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 238000007069 methylation reaction Methods 0.000 claims description 3
- WQIQNKQYEUMPBM-UHFFFAOYSA-N pentamethylcyclopentadiene Chemical compound CC1C(C)=C(C)C(C)=C1C WQIQNKQYEUMPBM-UHFFFAOYSA-N 0.000 claims description 3
- 150000003624 transition metals Chemical class 0.000 claims description 3
- MDTDQDVMQBTXST-UHFFFAOYSA-K 2h-inden-2-ide;titanium(4+);trichloride Chemical compound Cl[Ti+](Cl)Cl.C1=CC=C2[CH-]C=CC2=C1 MDTDQDVMQBTXST-UHFFFAOYSA-K 0.000 claims description 2
- NOQWABVRFAHTQD-UHFFFAOYSA-L [Cl-].[Cl-].C12=CC=CCC2CCC1[Zr+2]C1C2=CC=CCC2CC1 Chemical class [Cl-].[Cl-].C12=CC=CCC2CCC1[Zr+2]C1C2=CC=CCC2CC1 NOQWABVRFAHTQD-UHFFFAOYSA-L 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- QMBQEXOLIRBNPN-UHFFFAOYSA-L zirconocene dichloride Chemical compound [Cl-].[Cl-].[Zr+4].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 QMBQEXOLIRBNPN-UHFFFAOYSA-L 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- SNTMWYMKVGVJJJ-UHFFFAOYSA-L [Cl-].[Cl-].C12=CC=CC=C2C2=CC=CC=C2C1[Zr+2]C1C2=CC=CC=C2C2=CC=CC=C21 Chemical class [Cl-].[Cl-].C12=CC=CC=C2C2=CC=CC=C2C1[Zr+2]C1C2=CC=CC=C2C2=CC=CC=C21 SNTMWYMKVGVJJJ-UHFFFAOYSA-L 0.000 claims 1
- PVRIRQFFAWJTPS-UHFFFAOYSA-L [Cl-].[Cl-].C[Zr+2]C Chemical compound [Cl-].[Cl-].C[Zr+2]C PVRIRQFFAWJTPS-UHFFFAOYSA-L 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 229910000166 zirconium phosphate Inorganic materials 0.000 abstract description 3
- JWFYORYPRRVBPH-UHFFFAOYSA-J hydrogen phosphate;titanium(4+) Chemical compound [Ti+4].OP([O-])([O-])=O.OP([O-])([O-])=O JWFYORYPRRVBPH-UHFFFAOYSA-J 0.000 abstract 6
- QOKYJGZIKILTCY-UHFFFAOYSA-J hydrogen phosphate;zirconium(4+) Chemical compound [Zr+4].OP([O-])([O-])=O.OP([O-])([O-])=O QOKYJGZIKILTCY-UHFFFAOYSA-J 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 267
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 186
- 229910052757 nitrogen Inorganic materials 0.000 description 133
- 229910007928 ZrCl2 Inorganic materials 0.000 description 107
- 238000000746 purification Methods 0.000 description 104
- 239000011521 glass Substances 0.000 description 51
- 239000007788 liquid Substances 0.000 description 42
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 34
- 239000005977 Ethylene Substances 0.000 description 34
- 238000006243 chemical reaction Methods 0.000 description 34
- 230000000694 effects Effects 0.000 description 28
- 229910001220 stainless steel Inorganic materials 0.000 description 25
- 239000010935 stainless steel Substances 0.000 description 25
- 101000601429 Rattus norvegicus N-terminal EF-hand calcium-binding protein 1 Proteins 0.000 description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 18
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 17
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 17
- 239000007921 spray Substances 0.000 description 12
- 239000000725 suspension Substances 0.000 description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 11
- 238000004945 emulsification Methods 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 description 5
- 230000020477 pH reduction Effects 0.000 description 5
- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical class [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 4
- 229910010062 TiCl3 Inorganic materials 0.000 description 4
- 229910007926 ZrCl Inorganic materials 0.000 description 4
- 229910007930 ZrCl3 Inorganic materials 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- 229960001866 silicon dioxide Drugs 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 101000601423 Homo sapiens N-terminal EF-hand calcium-binding protein 2 Proteins 0.000 description 2
- 102100037704 N-terminal EF-hand calcium-binding protein 2 Human genes 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 230000037048 polymerization activity Effects 0.000 description 2
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 2
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 1
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- AQZWEFBJYQSQEH-UHFFFAOYSA-N 2-methyloxaluminane Chemical compound C[Al]1CCCCO1 AQZWEFBJYQSQEH-UHFFFAOYSA-N 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- SXFKDLMPPGKTTQ-UHFFFAOYSA-K C=C[Zr+3].[Cl-].[Cl-].[Cl-] Chemical compound C=C[Zr+3].[Cl-].[Cl-].[Cl-] SXFKDLMPPGKTTQ-UHFFFAOYSA-K 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- JDNRIXFOSWYYBA-UHFFFAOYSA-L [Cl-].[Cl-].C(=CC=CC)[Zr+2] Chemical compound [Cl-].[Cl-].C(=CC=CC)[Zr+2] JDNRIXFOSWYYBA-UHFFFAOYSA-L 0.000 description 1
- DNQSUKNLXAKXJJ-UHFFFAOYSA-L [Cl-].[Cl-].C[Zr+2](C1C=CC=C1)C1C2=CC=CC=C2C=2C=CC=CC1=2 Chemical compound [Cl-].[Cl-].C[Zr+2](C1C=CC=C1)C1C2=CC=CC=C2C=2C=CC=CC1=2 DNQSUKNLXAKXJJ-UHFFFAOYSA-L 0.000 description 1
- GOGBMDCBWLGVIT-UHFFFAOYSA-N [Zr].C1C=CC=C1 Chemical class [Zr].C1C=CC=C1 GOGBMDCBWLGVIT-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- ZMMRKRFMSDTOLV-UHFFFAOYSA-N cyclopenta-1,3-diene zirconium Chemical compound [Zr].C1C=CC=C1.C1C=CC=C1 ZMMRKRFMSDTOLV-UHFFFAOYSA-N 0.000 description 1
- QOXHZZQZTIGPEV-UHFFFAOYSA-K cyclopenta-1,3-diene;titanium(4+);trichloride Chemical compound Cl[Ti+](Cl)Cl.C=1C=C[CH-]C=1 QOXHZZQZTIGPEV-UHFFFAOYSA-K 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002220 fluorenes Chemical group 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- NVHYILYRFKJMBR-UHFFFAOYSA-N phenylphosphonic acid;zirconium Chemical compound [Zr].OP(O)(=O)C1=CC=CC=C1 NVHYILYRFKJMBR-UHFFFAOYSA-N 0.000 description 1
- 150000003017 phosphorus Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention provides a spherical supported metallocene catalyst. The carrier of the catalyst is spherical titanium hydrogen phosphate/zirconium compound, the main catalyst is metallocene compound, and the cocatalyst is methylaluminoxane; the spherical titanium hydrogen phosphate/zirconium compound comprises one or a combination of more of titanium hydrogen phosphate, modified titanium hydrogen phosphate and zirconium hydrogen phosphate. The invention also provides a preparation method of the spherical supported metallocene catalyst, application of the spherical supported metallocene catalyst in olefin polymerization, the spherical titanium hydrogen phosphate/zirconium compound and a preparation method of the spherical titanium hydrogen phosphate/zirconium compound. The spherical load type metallocene catalyst provided by the invention has higher catalytic activity, and the obtained polymer particles have good shapes.
Description
Technical field
The invention belongs to olefin polymerization catalysis fields, and in particular to a kind of spherical supported type metallocene catalyst.
Background technique
It can be traced using the application that Group IVB transition metal is the metallocene compound of center metal on catalysis in olefine polymerization
To in the early 1960s, US2924593 is disclosed using alkyl aluminum as co-catalyst, it is poly- to be catalyzed ethylene using bis cyclopentadienyl zirconium dichloride
It closes.Late 1970s, as to be found to can effectively improve metallocene compound catalyzed alkene poly- for methylaluminoxane (MAO)
The activity of conjunction is rapidly developed by the metallocene catalyst of system of metallocene compound-MAO: Hoechst company is in 20 generation
Record applied the beginning of the eighties high activity zirconocene catalyst and methyl alumoxane cocatalyst key patent (US4542199A,
US4544762A)；The nineteen eighty-two metallocene compound of chirality bridging is synthesized out (Journal of Organometallic
Chemistry,232(1982)233-247)；Exxon company in 1984 reports to be urged with ansa- [Et (Ind) 2TiCl2]/MAO
The polypropylene (J.Am.Chem.SOC.1984,106,6355-6364) that agent has obtained isotactic and randomly mixed, then manufacture etc.
First metallocene catalyst of isotactic polypropylene has been found (Angew.Chem.Inr.Ed.Enyl.24 (1985) No.6,507-
508)；Hoechst company obtains the patent (DE3835044A1) that cyclic olefine copolymer is prepared using metallocene catalyst.
Idemitsu company has manufactured syndiotactic polytyrene by single metallocene catalyst, and has applied for patent (EP0210615A2)；
There is the cyclopentadiene zirconium compounds of the bridging with fluorenes ring of Cs symmetry for 1988 in Fina company report
(J.Am.Chem.SOC.1988,110,6255-6256), such metallocene compound can be catalyzed propylene syndiotactic polymerization, Fina
Company obtains the patent (EP0351391A2, EP0351392) of the metallocene catalyst and syndiotactic polypropylene；Constrained geometry
The metallocene compound of structure is reported (Organometallics 1990,9,867-869) for the first time in nineteen ninety, Ji Hutong
When, Exxon company (EP0420436A1), Dow company (EP0416815A2) propose constrained geometry metallocene catalyst
Patent.
In metallocene catalyst system, the slight change of ligand structure can cause the huge of catalyst catalytic performance to change
Become, can be obtained by adjusting the structure of catalyst ligand to achieve the effect that traditional Zeigler-Natta catalyst cannot achieve
To the polyolefin products of different performance.Although but metallocene catalyst has compared with traditional Ziegler-Natta catalyst
Unique performance, but since unsupported metallocene catalyst is in catalysis in olefine polymerization, the form of product is difficult to control, and exists
Serious viscous kettle phenomenon, significantly limit it in the application of industrial circle.
In order to improve the form of polymer, the bulk density of polymer is improved, and the particle for being easier to control polymer is big
Small distribution makes metallocene catalyst be suitable for existing olefinic polymerization device and technique, and the method for being easier to realize is Jiang Maojin
Metal catalyst system is supported, and such technology is applied on metallocene catalyst, promotes metallocene catalyst
Industrial application.There are many carrier that can be used for metallocene calalyst for polymerization of olefine, and common carrier is mainly silica-gel carrier (SiO2),
There are a large amount of article, patent to disclose carried metallocene catalyst (the Journal of Polymer using silica gel as carrier
Science:Part A Polymer Chemistry,Vol.33,2093-2108(1995)；US5635437A), furthermore molecule
Sieve (Science 285,2113 (1999), montmorillonite (Polym.Int., 2009,58,1319-1325), polystyrene
Materials such as (Macromol.Rapid Commun., 16,821-830 (1995)) are also done the load of carried metallocene catalyst
Body, but silica gel is compared, these materials all Shortcomings, thus it is current still based on silica-gel carrier in industrial application.
Summary of the invention
In order to overcome the above problem, the object of the present invention is to provide a kind of spherical supported type metallocene catalyst, the catalysis
Agent shows good catalytic activity in olefin polymerization.
It is a further object of the present invention to provide a kind of preparation methods of above-mentioned spherical supported type metallocene catalyst.
It is a further object of the present invention to provide the application of above-mentioned spherical supported type metallocene catalyst in olefin polymerization.
It is a further object of the present invention to provide as made from above-mentioned spherical supported type metallocene catalyst catalysis in olefine polymerization
Polyolefin-nanocomposite.
It is a further object of the present invention to provide spherical phosphoric acid hydrogen titanium/zirconiums for above-mentioned spherical supported type metallocene catalyst
Class compound carrier.
It is a further object of the present invention to provide a kind of preparation methods of above-mentioned spherical phosphoric acid hydrogen titanium/Zirconium compound carrier.
In order to achieve the above objectives, the present invention provides a kind of spherical supported type metallocene catalysts, wherein the catalyst
Carrier be spherical phosphoric acid hydrogen titanium/Zirconium compound, the major catalyst of the catalyst is metallocene compound, the catalyst
Co-catalyst be methylaluminoxane；
The spherical shape phosphoric acid hydrogen titanium/Zirconium compound includes phosphoric acid hydrogen titanium (Ti (HPO4)2), modified phosphate hydrogen titanium and phosphoric acid
Hydrogen zirconium (Zr (HPO4)2) one or more of combination；
The content of the central metal of the metallocene compound in the catalyst is 0.1wt%-0.4wt%, described
Aluminium content in catalyst is 5wt%-20wt%.
Phosphoric acid hydrogen titanium/Zirconium compound is a kind of acid clay class material, including phosphoric acid hydrogen titanium, phosphoric acid hydrogen zirconium, organic phosphine
Sour hydrogen titanium (such as phenyl-phosphonic acid titanium) passes through organically-modified phosphoric acid hydrogen titanium (such as phosphniline of the methods of co-precipitation or ion exchange preparation
Acid-phosphoric acid hydrogen titanium), pass through strong acid or the acidified modified titanium phosphate of middle strong acid treatment (such as sulfuric acid is acidified phosphoric acid hydrogen titanium).Phosphoric acid hydrogen
Titanium/Zirconium compound has layer structure and stronger acidity, leads in ion exchange, intercalation material, rubber-plastics material additive etc.
Domain has potential application.
For the carrier of polyolefin catalyst, it is considered that, the substance of polyolefin catalyst carrier is used as in screening
When, Ying Jinliang avoids the substance for selecting surface to contain excessive hydroxyl.Because hydroxyl is Bronsted acid, when the surface of carrier is contained greatly
When measuring hydroxyl, hydroxyl is easy to act on the ligand of metallocene catalyst, so that being allowed to split away off from catalyst causes to urge
Agent inactivates (Macromolecules 1992,25,1780-1785).Such as in the prior art, exist organic benzenephosphonic acid
Zirconium (α-Zr (O3PPh)2) relevant report as olefin polymerization catalysis made from carrier loaded metallocene (CN101580561),
Carrier in the patent is the substance after the hydroxyl in phosphoric acid hydrogen zirconium is substituted by phenyl, and replaces purpose to be in order to avoid hydroxyl presence
And the phenomenon that causing part metallocene catalyst to decompose, but gathered organic benzene, organic basic zirconium phosphate as catalyst made of carrier
It is less desirable to close activity.For scheme provided by the invention compared with the above-mentioned prior art, the carrier in the present invention can be selected from phosphoric acid
Hydrogen titanium, modified phosphate hydrogen titanium and phosphoric acid hydrogen zirconium.By the test of some column, inventor discovery: (1) unsubstituted phosphoric acid hydrogen titanium/
Zirconium (hydroxyl is fully retained) or partially substituted phosphoric acid hydrogen titanium (hydroxylic moiety reservation) are being used as olefin polymerization catalysis load
When body, the polymerization activity of catalyst is not that can reduce catalytic activity as enlightening in the prior art or even cause to inactivate,
So that catalyst is provided with unexpected high catalytic activity instead, (generation of above-mentioned phenomenon may be with phosphoric acid hydrogen titanium/zirconium class chemical combination
The physicochemical properties of object are related)；(2) support type cyclopentadienyl transition metal made of after the hydroxyl in phosphoric acid hydrogen titanium is fully substituted is urged
Agent, compared with the carried metallocene catalyst made of the organic benzene, organic basic zirconium phosphate in the prior art, it is very good to be of virtually
Catalytic activity.
In above-mentioned spherical supported type metallocene catalyst, it is preferable that the modified phosphate hydrogen titanium includes organically-modified phosphorus
(hydroxyl in phosphoric acid hydrogen titanium is partially replaced or is completely replaced compound to sour hydrogen titanium, and preferably hydroxyl is partially substituted
Compound) or acidified modified titanium phosphate；It is further preferred that the organically-modified phosphoric acid hydrogen titanium includes benzenephosphonic acid titanium (Ti
(C6H5PO3)2) and phenyl-phosphonic acid-phosphoric acid hydrogen titanium (Ti (C6H5PO3)x(HPO4)2-x, 0 < x < 2 is preferably 0.5≤x≤1.5)；It is more excellent
Selection of land, the acidified modified titanium phosphate include sulfuric acid acidification phosphoric acid hydrogen titanium.
In above-mentioned spherical supported type metallocene catalyst, it is preferable that the central metal of the metallocene compound is IVB
Group 4 transition metal；The central metal is preferably titanium, zirconium or hafnium.
It is further preferred that the metallocene compound includes non-bridged dis-cyclopentadiene compounds, non-bridged Monodentate compound, contains
The combination of the metallocene compound and one or more of constrained geometry metallocene compound of bridging.
In above-mentioned spherical supported type metallocene catalyst, it is preferable that the non-bridged dis-cyclopentadiene compounds include: dichloro two
Luxuriant zirconium Cp2ZrCl2, two indenyl zirconium Ind of dichloro2ZrCl2, bis- (butyl cyclopentadienyl group) zirconium dichlorides (BuCp)2ZrCl2, fluorenyl
Cyclopentadienyl zirconium dichloride FluCpZrCl2, dichloro hafnocene Cp2HfCl2, bis- (butyl cyclopentadienyl group) hafnium dichlorides
(BuCp)2HfCl2Or bis- (butyl cyclopentadienyl group) di-methylation hafniums (BuCp)2Hf(CH3)2)。
In above-mentioned spherical supported type metallocene catalyst, it is preferable that the non-bridged Monodentate compound includes: ring penta 2
Alkenyl titanium trichloride CpTiCl3, indenyl titanium trichloride IndTiCl3, pentamethylcyclopentadiene base titanium trichloride Cp*TiCl3Or five
Methyl cyclopentadienyl tri-chlorination zirconium Cp*ZrCl3)。
In above-mentioned spherical supported type metallocene catalyst, it is preferable that the metallocene compound containing bridging includes:
Bis- (penta bicycloenyl of ring) the silicon substrate zirconium dichloride Me of dimethyl2SiCp2ZrCl2, bis- (9- fluorenyl) the silicon substrate zirconium dichlorides of dimethyl
Me2Si(9-Flu)2ZrCl2, bis- (9- fluorenyl) the zirconium dichloride iPr (9-Flu) of isopropyl subunit2ZrCl2, isopropyl subunit cyclopentadiene
Base (9- fluorenyl) zirconium dichloride iPrCp (9-Flu) ZrCl2, diphenyl methylene cyclopentadienyl group (9- fluorenyl) zirconium dichloride Ph2CCp
(9-Flu)ZrCl2, the double tetrahydroindenyl zirconium dichloride rac-EtInd of rac- vinyl2ZrCl2, bis- (tetrahydro indenyls) two of rac- vinyl
Zirconium chloride rac-Et (IndH4)2ZrCl2, bis- (2- methyl -4,5- benzo indenyl) the silicon substrate zirconium dichloride rac- of rac- dimethyl
Me2Si(2-Me-4,5-BenzInd)2ZrCl2Or bis- (2- methyl 4-phenyl indenyl) the silicon substrate zirconium dichloride rac- of rac- dimethyl
Me2Si(2-Me-4-PhInd)2ZrCl2。
In above-mentioned spherical supported type metallocene catalyst, it is preferable that the constrained geometry metallocene compound packet
It includes: [Me2Si(Me4Cp)(NtBu)]TiCl2。
Invention additionally provides a kind of preparation method of above-mentioned spherical supported type metallocene catalyst, this method include with
Lower step:
By spherical phosphoric acid hydrogen titanium/Zirconium compound support dispersion in toluene, methylaluminoxane processing is added, is activated
Spherical phosphoric acid hydrogen titanium/Zirconium compound carrier；
Metallocene compound is dissolved in toluene, methylaluminoxane processing, the metallocene compound activated is added
Solution；
Spherical phosphoric acid hydrogen titanium/Zirconium compound carrier of above-mentioned activation is mixed with the metallocene compound solution of activation,
Then agitated processing obtains mixed system, and mixed system is washed, solid sediment is obtained by filtration, and solid sediment is through drying
Obtain spherical supported type metallocene catalyst.
In the preparation method of above-mentioned spherical supported type metallocene catalyst, it is preferable that the metallocene compound and ball
Shape phosphoric acid hydrogen titanium/Zirconium compound carrier mass ratio is 0.01-0.03:1.
In the preparation method of above-mentioned spherical supported type metallocene catalyst, it is preferable that in the spherical phosphoric acid of preparation activation
In the step of hydrogen titanium/Zirconium compound carrier, the mole of methylaluminoxane is in terms of aluminium, methylaluminoxane and spherical phosphoric acid hydrogen
Titanium/Zirconium compound carrier amount ratio is 3-9mmol/g.
In the preparation method of above-mentioned spherical supported type metallocene catalyst, it is preferable that in the metallocene of preparation activation
In the step of polymer solution, in terms of aluminium, the amount ratio of methylaluminoxane and metallocene compound is the mole of methylaluminoxane
0.015-0.3mol/g。
In the preparation method of above-mentioned spherical supported type metallocene catalyst, it is preferable that at the addition methylaluminoxane
The condition of reason are as follows: at 20 DEG C -50 DEG C, stir 20 minutes to 2 hours.
In the preparation method of above-mentioned spherical supported type metallocene catalyst, it is preferable that the condition of the stir process are as follows:
At 20 DEG C -50 DEG C, stir 30 minutes to 3 hours.
In the preparation method of above-mentioned spherical supported type metallocene catalyst, it is preferable that the solvent of the washing is first
Benzene or hexane.
In the preparation method of above-mentioned spherical supported type metallocene catalyst, it is preferable that in the spherical phosphoric acid of preparation activation
It when hydrogen titanium/Zirconium compound carrier and/or the metallocene compound solution of activation, is carried out under inert gas shielding.
The present invention also provides the application of above-mentioned spherical supported type metallocene catalyst in olefin polymerization.
The present invention also provides the polyolefin-as made from above-mentioned spherical supported type metallocene catalyst catalysis in olefine polymerization to receive
Nano composite material, wherein in the polyolefin-nanocomposite, phosphoric acid hydrogen titanium/Zirconium compound is dispersed with nanoscale
In a polymer matrix.
The present invention also provides a kind of spherical phosphoric acid hydrogen titanium/zirconium classes for above-mentioned spherical supported type metallocene catalyst
Close object carrier, wherein the spherical shape phosphoric acid hydrogen titanium/Zirconium compound includes phosphoric acid hydrogen titanium, modified phosphate hydrogen titanium and phosphoric acid hydrogen zirconium
One or more of combination；The shape of the spherical shape phosphoric acid hydrogen titanium/Zirconium compound carrier is microspheroidal, and average grain diameter is
5-50 μm, specific surface 100-400m2/ g, specific pore volume 0.8-1.6cc/g.
Spherical shape phosphoric acid hydrogen titanium/Zirconium compound carrier provided by the invention has preferable spherical morphology, is obtained with this
Spherical supported type catalyst is used for the preferable polymer beads of the available form of olefinic polymerization, is conducive to polymer in reactor
In transmission, avoid viscous kettle or adhesion pipeline.
In above-mentioned spherical phosphoric acid hydrogen titanium/Zirconium compound carrier, it is preferable that the modified phosphate hydrogen titanium includes organic changes
Property phosphoric acid hydrogen titanium (hydroxyl in phosphoric acid hydrogen titanium partially replaced or replaced completely after compound) or acidified modified titanium phosphate；
It is further preferred that the organically-modified phosphoric acid hydrogen titanium includes benzenephosphonic acid titanium (Ti (C6H5PO3)2) and phenyl-phosphonic acid-phosphoric acid hydrogen titanium
(Ti(C6H5PO3)x(HPO4)2-x, 0 < x < 2, preferably 0.5≤x≤1.5)；It is highly preferred that the acidified modified titanium phosphate packet
Include sulfuric acid acidification phosphoric acid hydrogen titanium.
The present invention also provides a kind of preparation methods of above-mentioned spherical phosphoric acid hydrogen titanium/Zirconium compound carrier, wherein the party
Method the following steps are included:
Phosphoric acid hydrogen titanium/Zirconium compound and water are matched into resulting mixture, phosphoric acid hydrogen titanium/Zirconium compound and water in mixture
Mass ratio is 0.05-0.2；The mixture is emulsified, phosphoric acid hydrogen titanium/Zirconium compound slurries are obtained；
The phosphoric acid hydrogen titanium/Zirconium compound slurries are spray-dried, spherical phosphoric acid hydrogen titanium/Zirconium compound is obtained
Particle；
The spherical phosphoric acid hydrogen titanium/Zirconium compound particle is subjected to vacuum dehydration processing at 100 DEG C -200 DEG C,
Then it is cooled to room temperature under inert atmosphere protection, obtains spherical phosphoric acid hydrogen titanium/Zirconium compound carrier.
In the preparation method of above-mentioned spherical phosphoric acid hydrogen titanium/Zirconium compound carrier, it is preferable that the mixture is carried out cream
When change, emulsification cutter can be selected and emulsified.
It is provided by the invention to be urged as spherical phosphoric acid hydrogen titanium/Zirconium compound as spherical supported type metallocene made from carrier
Agent has polymerization activity high, and co-catalyst dosage is few when polymerization, the good advantage of morphology.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of spherical phosphoric acid hydrogen titanium carrier prepared by embodiment 1；
Fig. 2 is the scanning electron microscope (SEM) photograph of spherical supported type metallocene catalyst prepared by embodiment 13；
Fig. 3 is the scanning electron microscope (SEM) photograph for the polyethylene that embodiment 13 obtains；
Fig. 4 is the polyacrylic scanning electron microscope (SEM) photograph that embodiment 28 obtains；
Fig. 5 is the polyacrylic transmission electron microscope picture that embodiment 28 obtains.
Specific embodiment
In order to which technical characteristic of the invention, purpose and beneficial effect are more clearly understood, now to skill of the invention
Art scheme carries out described further below, but should not be understood as that limiting the scope of the invention.
Embodiment 1
Present embodiments provide a kind of spherical phosphoric acid hydrogen titanium carrier, the specific preparation process of above-mentioned carrier are as follows:
It is accurate to measure 20g phosphoric acid hydrogen titanium Ti (HPO4)2, 100g deionized water is added, handles the mixture with emulsification pretreatment machine
System, rotor speed 10000rpm handle time 30min, obtain white " milky " phosphoric acid hydrogen titanium suspension；
Phosphoric acid hydrogen titanium suspension is formed by spray dryer, spray dryer inlet temperature is 190 DEG C, outlet
Temperature is 110 DEG C；
It will obtain after solid powder is heated to 160 DEG C of vacuum drying treatment 6h, cooled to room temperature under nitrogen protection obtains
To spherical phosphoric acid hydrogen titanium carrier product, it is denoted as sTiP-1 (scanning electron microscope (SEM) photograph that Fig. 1 is sTiP-1).
Embodiment 2
Present embodiments provide a kind of spherical phosphoric acid hydrogen titanium carrier, the specific preparation process of above-mentioned carrier are as follows:
It is accurate to measure 10g phosphoric acid hydrogen titanium Ti (HPO4)2, 100g deionized water is added, handles the mixture with emulsification pretreatment machine
System, rotor speed 10000rpm handle time 30min, obtain white " milky " phosphoric acid hydrogen titanium suspension；
Phosphoric acid hydrogen titanium suspension is formed by spray dryer, spray dryer inlet temperature is 200 DEG C, outlet
Temperature is 100 DEG C；
It will obtain after solid powder is heated to 140 DEG C of vacuum drying treatment 6h, cooled to room temperature under nitrogen protection obtains
To spherical phosphoric acid hydrogen titanium carrier product, it is denoted as sTiP-2.
Embodiment 3
Present embodiments provide a kind of spherical phenyl-phosphonic acid titanium carrier, the specific preparation process of above-mentioned carrier are as follows:
It is accurate to measure 5g phenyl-phosphonic acid titanium Ti (C6H5PO3)2, 100g deionized water is added, handles the mixing with emulsification pretreatment machine
Objects system, rotor speed 8000rpm handle time 30min, obtain white " milky " phenyl-phosphonic acid titanium suspension；
Phenyl-phosphonic acid titanium suspension is formed by spray dryer, spray dryer inlet temperature is 180 DEG C, outlet
Temperature is 120 DEG C；
It will obtain after solid powder is heated to 100 DEG C of vacuum drying treatment 4h, cooled to room temperature under nitrogen protection obtains
To spherical phenyl-phosphonic acid titanium carrier product, it is denoted as sTiBP.
Embodiment 4
Present embodiments provide a kind of spherical phenyl-phosphonic acid-phosphoric acid hydrogen titanium carrier, the specific preparation process of above-mentioned carrier are as follows:
It is accurate to measure 10g phenyl-phosphonic acid titanium Ti (C6H5PO3)(HPO4), 100g deionized water is added, is handled with emulsification pretreatment machine
The mixture system, rotor speed 8000rpm handle time 60min, obtain white " milky " phenyl-phosphonic acid titanium suspension；
Phenyl-phosphonic acid titanium suspension is formed by spray dryer, spray dryer inlet temperature is 180 DEG C, outlet
Temperature is 120 DEG C；
It will obtain after solid powder is heated to 150 DEG C of vacuum drying treatment 4h, cooled to room temperature under nitrogen protection obtains
To spherical phenyl-phosphonic acid-phosphoric acid hydrogen titanium carrier product, it is denoted as sTiBPHP.
Embodiment 5
Present embodiments provide a kind of spherical sulfuric acid acidification phosphoric acid hydrogen titanium carrier, the specific preparation process of above-mentioned carrier are as follows:
It is accurate to measure 15g phosphoric acid hydrogen titanium Ti (HPO4)2, 30% aqueous sulfuric acid of 150ml is added, is dispersed with stirring uniformly, and
95 DEG C are heated to, the reaction was continued for 24 hours；End of reaction is down to room temperature, and filtration product is washed with deionized；To product (sulfuric acid acid
Change phosphoric acid hydrogen titanium) in be added 100g deionized water；The mixture system is handled with emulsification pretreatment machine, rotor speed is
10000rpm handles time 30min, obtains white " milky " sulfuric acid acidification phosphoric acid hydrogen titanium suspension；
Sulfuric acid acidification phosphoric acid hydrogen titanium suspension is formed by spray dryer, spray dryer inlet temperature is
200 DEG C, outlet temperature is 120 DEG C；
It will obtain after solid powder is heated to 200 DEG C of vacuum drying treatment 4h, cooled to room temperature under nitrogen protection obtains
Phosphoric acid hydrogen titanium products are acidified to spherical sulfuric acid, are denoted as sTiP-S.
Embodiment 6
Present embodiments provide a kind of spherical phosphoric acid hydrogen zirconium carrier, the specific preparation process of above-mentioned carrier are as follows:
It is accurate to measure 20g phosphoric acid hydrogen titanium Zr (HPO4)2, 90g deionized water is added, handles the mixture with emulsification pretreatment machine
System, rotor speed 8000rpm handle time 30min, obtain white " milky " phosphoric acid hydrogen titanium suspension；
Phosphoric acid hydrogen titanium suspension is formed by spray dryer, spray dryer inlet temperature is 180 DEG C, outlet
Temperature is 120 DEG C；
It will obtain after solid powder is heated to 150 DEG C of vacuum drying treatment 6h, cooled to room temperature under nitrogen protection obtains
To spherical phosphoric acid hydrogen zirconium vector product, it is denoted as sZrP.
Embodiment 7
A kind of spherical supported type metallocene catalyst is present embodiments provided, is the carrier loaded dichloro two with embodiment 1
Luxuriant zirconium Cp2ZrCl2It is obtained, specific preparation process are as follows:
It accurately weighs in the glass reactor that 5g sTiP-1 is transferred to after nitrogen is sufficiently displaced from, adds under nitrogen protection
Enter the toluene 25ml of water removal purification；After stirring makes it be uniformly dispersed, it is added 10ml methylaluminoxane (toluene solution of 1.5M), in
20 DEG C of stirring 20min, the carrier activated.
100mg Cp is accurately weighed under nitrogen protection2ZrCl2The glass reactor being transferred to after nitrogen is sufficiently displaced from
In, the toluene 15ml of water removal purification is added；After stirring to dissolve completely, 1ml methylaluminoxane is added, and (toluene of 1.5M is molten
Liquid), in 20 DEG C of stirrings 20min, the Cp activated2ZrCl2Solution.
Under nitrogen protection by the Cp of activation2ZrCl2Solution is added in the carrier of activation, in 20 DEG C of stirring 30min；Reaction
After, it stands, filters out liquid after layering, washed twice with the toluene of 20ml water removal purification, then remove water oneself of purification with 30ml
Alkane washes twice；Solid is dried in vacuo, spherical supported type metallocene catalyst is obtained and (is denoted as sTiP-1-Cp2ZrCl2)。
In 2L stainless steel polymerization autoclave, after being sufficiently displaced from ethylene, the hexane of 1L water removal purification is added, 2ml is added
Triethyl aluminum (hexane solution of 2.4M), is subsequently added into 100mg catalyst sTiP-1-Cp2ZrCl2, it is passed through ethylene, by pressure liter
Height simultaneously maintains 1.0MPa, reacts 1 hour at 60 DEG C；The activity for measuring catalyst is 330gPE/gcath.
Embodiment 8
A kind of spherical supported type metallocene catalyst is present embodiments provided, is the carrier loaded dichloro two with embodiment 2
Luxuriant zirconium Cp2ZrCl2It is obtained, specific preparation process are as follows:
It accurately weighs in the glass reactor that 5g sTiP-2 is transferred to after nitrogen is sufficiently displaced from, adds under nitrogen protection
Enter the toluene 25ml of water removal purification；After stirring makes it be uniformly dispersed, it is added 30ml methylaluminoxane (toluene solution of 1.5M), in
50 DEG C of stirring 2h, the carrier activated.
150mg Cp is accurately weighed under nitrogen protection2ZrCl2The glass reactor being transferred to after nitrogen is sufficiently displaced from
In, the toluene 15ml of water removal purification is added；After stirring to dissolve completely, 3ml methylaluminoxane is added, and (toluene of 1.5M is molten
Liquid), in 50 DEG C of stirrings 2h, the Cp activated2ZrCl2Solution.
Under nitrogen protection by the Cp of activation2ZrCl2Solution is added in the carrier of activation, in 50 DEG C of stirring 3h；Reaction terminates
Afterwards, it stands, filters out liquid after layering, washed twice with the toluene of 20ml water removal purification, then washed with the hexane of 30ml water removal purification
It washs twice；Solid is dried in vacuo, spherical supported type metallocene catalyst is obtained and (is denoted as sTiP-2-Cp2ZrCl2)。
In 2L stainless steel polymerization autoclave, after being sufficiently displaced from ethylene, the hexane of 1L water removal purification is added, 2ml is added
Triethyl aluminum (hexane solution of 2.4M), is subsequently added into 100mg catalyst sTiP-2-Cp2ZrCl2, it is passed through ethylene, by pressure liter
Height simultaneously maintains 1.0MPa, reacts 1 hour at 60 DEG C；The activity for measuring catalyst is 400gPE/gcath.
Embodiment 9
A kind of spherical supported type metallocene catalyst is present embodiments provided, is the carrier loaded dichloro two with embodiment 3
Luxuriant zirconium Cp2ZrCl2It is obtained, specific preparation process are as follows:
It accurately weighs in the glass reactor that 5g sTiBP is transferred to after nitrogen is sufficiently displaced from, is added under nitrogen protection
Remove water the toluene 25ml of purification；After stirring makes it be uniformly dispersed, it is added 25ml methylaluminoxane (toluene solution of 1.5M), in 30
DEG C stirring 1h, the carrier activated.
100mg Cp is accurately weighed under nitrogen protection2ZrCl2The glass reactor being transferred to after nitrogen is sufficiently displaced from
In, the toluene 15ml of water removal purification is added；After stirring to dissolve completely, 20ml methylaluminoxane is added, and (toluene of 1.5M is molten
Liquid), in 30 DEG C of stirrings 1h, the Cp activated2ZrCl2Solution.
Under nitrogen protection by the Cp of activation2ZrCl2Solution is added in the carrier of activation, in 40 DEG C of stirring 2h；Reaction terminates
Afterwards, it stands, filters out liquid after layering, washed twice with the toluene of 20ml water removal purification, then washed with the hexane of 30ml water removal purification
It washs twice；Solid is dried in vacuo, spherical supported type metallocene catalyst is obtained and (is denoted as sTiBP-Cp2ZrCl2)。
In 2L stainless steel polymerization autoclave, after being sufficiently displaced from ethylene, the hexane of 1L water removal purification is added, 2ml is added
Triethyl aluminum (hexane solution of 2.4M), is subsequently added into 100mg catalyst sTiBP-Cp2ZrCl2, it is passed through ethylene, by pressure rise
And 1.0MPa is maintained, it is reacted 1 hour at 60 DEG C.The activity for measuring catalyst is 120gPE/gcath.
Embodiment 10
A kind of spherical supported type metallocene catalyst is present embodiments provided, is the carrier loaded dichloro two with embodiment 4
Luxuriant zirconium Cp2ZrCl2It is obtained, specific preparation process are as follows:
It accurately weighs in the glass reactor that 5g sTiBPHP is transferred to after nitrogen is sufficiently displaced from, adds under nitrogen protection
Enter the toluene 25ml of water removal purification；After stirring makes it be uniformly dispersed, it is added 16ml methylaluminoxane (toluene solution of 1.5M), in
30 DEG C of stirring 1h, the carrier activated.
100mg Cp is accurately weighed under nitrogen protection2ZrCl2The glass reactor being transferred to after nitrogen is sufficiently displaced from
In, the toluene 15ml of water removal purification is added；After stirring to dissolve completely, 2ml methylaluminoxane is added, and (toluene of 1.5M is molten
Liquid), in 30 DEG C of stirrings 1h, the Cp activated2ZrCl2Solution.
Under nitrogen protection by the Cp of activation2ZrCl2Solution is added in the carrier of activation, in 40 DEG C of stirring 2h；Reaction terminates
Afterwards, it stands, filters out liquid after layering, washed twice with the toluene of 20ml water removal purification, then washed with the hexane of 30ml water removal purification
It washs twice；Solid is dried in vacuo, spherical supported type metallocene catalyst is obtained and (is denoted as sTiBPHP-Cp2ZrCl2)。
In 2L stainless steel polymerization autoclave, after being sufficiently displaced from ethylene, the hexane of 1L water removal purification is added, 2ml is added
Triethyl aluminum (hexane solution of 2.4M), is subsequently added into 100mg catalyst sTiBPHP-Cp2ZrCl2, it is passed through ethylene, by pressure liter
Height simultaneously maintains 1.0MPa, reacts 1 hour at 60 DEG C；The activity for measuring catalyst is 220gPE/gcath.
Embodiment 11
A kind of spherical supported type metallocene catalyst is present embodiments provided, is the carrier loaded dichloro two with embodiment 5
Luxuriant zirconium Cp2ZrCl2It is obtained, specific preparation process are as follows:
It accurately weighs in the glass reactor that 5g sTiP-S is transferred to after nitrogen is sufficiently displaced from, adds under nitrogen protection
Enter the toluene 25ml of water removal purification；After stirring makes it be uniformly dispersed, it is added 16ml methylaluminoxane (toluene solution of 1.5M), in
30 DEG C of stirring 1h, the carrier activated.
50mg Cp is accurately weighed under nitrogen protection2ZrCl2It is transferred in the glass reactor after nitrogen is sufficiently displaced from,
The toluene 15ml of water removal purification is added；After stirring to dissolve completely, it is added 1ml methylaluminoxane (toluene solution of 1.5M),
In 30 DEG C of stirrings 1h, the Cp activated2ZrCl2Solution.
Under nitrogen protection by the Cp of activation2ZrCl2Solution is added in the carrier of activation, in 40 DEG C of stirring 2h；Reaction terminates
Afterwards, it stands, filters out liquid after layering, washed twice with the toluene of 20ml water removal purification, then washed with the hexane of 30ml water removal purification
It washs twice；Solid is dried in vacuo, spherical supported type metallocene catalyst is obtained and (is denoted as sTiP-S-Cp2ZrCl2)。
In 2L stainless steel polymerization autoclave, after being sufficiently displaced from ethylene, the hexane of 1L water removal purification is added, 2ml is added
Triethyl aluminum (hexane solution of 2.4M), is subsequently added into 100mg catalyst sTiP-S-Cp2ZrCl2, it is passed through ethylene, by pressure liter
Height simultaneously maintains 1.0MPa, reacts 1 hour at 60 DEG C；The activity for measuring catalyst is 500gPE/gcath.
Embodiment 12
A kind of spherical supported type metallocene catalyst is present embodiments provided, is the carrier loaded dichloro two with embodiment 1
Indenyl zirconium Ind2ZrCl2It is obtained, specific preparation process are as follows:
It accurately weighs in the glass reactor that 5g sTiP-1 is transferred to after nitrogen is sufficiently displaced from, adds under nitrogen protection
Enter the toluene 25ml of water removal purification；After stirring makes it be uniformly dispersed, it is added 16ml methylaluminoxane (toluene solution of 1.5M), in
30 DEG C of stirring 1h, the carrier activated.
60mg Ind is accurately weighed under nitrogen protection2ZrCl2The glass reactor being transferred to after nitrogen is sufficiently displaced from
In, the toluene 15ml of water removal purification is added；After stirring to dissolve completely, 1ml methylaluminoxane is added, and (toluene of 1.5M is molten
Liquid), in 30 DEG C of stirrings 1h, the Ind activated2ZrCl2Solution.
Under nitrogen protection by the Ind of activation2ZrCl2Solution is added in the carrier of activation, in 40 DEG C of stirring 2h；Reaction knot
Shu Hou stands, filters out liquid after layering, is washed twice with the toluene of 20ml water removal purification, then the hexane refined with 30ml water removal
It washes twice；Solid is dried in vacuo, spherical supported type metallocene catalyst is obtained and (is denoted as sTiP-1-Ind2ZrCl2)。
In 2L stainless steel polymerization autoclave, after being sufficiently displaced from ethylene, the hexane of 1L water removal purification is added, 2ml is added
Triethyl aluminum (hexane solution of 2.4M), is subsequently added into 100mg catalyst sTiP-1-Ind2ZrCl2, it is passed through ethylene, by pressure liter
Height simultaneously maintains 1.0MPa, reacts 1 hour at 60 DEG C；The activity for measuring catalyst is 530gPE/gcath.
Embodiment 13
A kind of spherical supported type metallocene catalyst is present embodiments provided, is carrier loaded bis- (positive fourths with embodiment 1
Cyclopentadienyl group) zirconium dichloride (nBuCp)2ZrCl2It is obtained, specific preparation process are as follows:
It accurately weighs in the glass reactor that 5g sTiP-1 is transferred to after nitrogen is sufficiently displaced from, adds under nitrogen protection
Enter the toluene 25ml of water removal purification；After stirring makes it be uniformly dispersed, it is added 16ml methylaluminoxane (toluene solution of 1.5M), in
40 DEG C are stirred 1 hour, the carrier activated.
70mg (nBuCp) is accurately weighed under nitrogen protection2ZrCl2It is transferred to the reaction of the glass after nitrogen is sufficiently displaced from
In device, the toluene 10ml of water removal purification is added, stirs to dissolve；It is added 1ml methylaluminoxane (toluene solution of 1.5M), in
40 DEG C of stirrings 1h, (nBuCp) activated2ZrCl2Solution.
Under nitrogen protection by (nBuCp) of activation2ZrCl2Solution is added in the carrier of activation, stirs 2 hours in 40 DEG C；
After reaction, it stands, filters out liquid after layering, washed twice with the toluene of 20ml water removal purification, then removed water and refined with 30ml
Hexane wash twice.Solid is dried in vacuo, spherical supported type metallocene catalyst is obtained and (is denoted as sTiP-1- (nBuCp)2ZrCl2, scanning electron microscope (SEM) photograph is as shown in Figure 2).
In 2L stainless steel polymerization autoclave, after being sufficiently displaced from ethylene, the hexane of 1L water removal purification is added, 2ml is added
Triethyl aluminum (hexane solution of 2.4M), is subsequently added into 100mg catalyst sTiP-1- (nBuCp)2ZrCl2, it is passed through ethylene, will be pressed
Power increases and maintains 1.0MPa, in 60 DEG C of reactions, 1 hour (its scanning electron microscope (SEM) photograph such as Fig. 3 institute of obtained polyethylene product
Show)；The activity for measuring catalyst is 2300gPE/gcath.
Embodiment 14
A kind of spherical supported type metallocene catalyst is present embodiments provided, is the carrier loaded fluorenyl ring with embodiment 1
Pentadienyl zirconium dichloride FluCpZrCl2It is obtained, specific preparation process are as follows:
It accurately weighs in the glass reactor that 5g sTiP-1 is transferred to after nitrogen is sufficiently displaced from, adds under nitrogen protection
Enter the toluene 25ml of water removal purification；After stirring makes it be uniformly dispersed, it is added 16ml methylaluminoxane (toluene solution of 1.5M), in
40 DEG C are stirred 1 hour, the carrier activated.
100mg FluCpZrCl is accurately weighed under nitrogen protection2It is transferred to the reaction of the glass after nitrogen is sufficiently displaced from
In device, the toluene 10ml of water removal purification is added, stirs to dissolve；It is added 1ml methylaluminoxane (toluene solution of 1.5M), in
40 DEG C of stirrings 1h, the FluCpZrCl activated2Solution.
Under nitrogen protection by the FluCpZrCl of activation2Solution is added in the carrier of activation, stirs 2 hours in 40 DEG C；Instead
It after answering, stands, filters out liquid after layering, washed twice with the toluene of 20ml water removal purification, then refined with 30ml water removal
Hexane washes twice；Solid is dried in vacuo, spherical supported type metallocene catalyst is obtained and (is denoted as sTiP-1-
FluCpZrCl2)。
In 2L stainless steel polymerization autoclave, after being sufficiently displaced from ethylene, the hexane of 1L water removal purification is added, 2ml is added
Triethyl aluminum (hexane solution of 2.4M), is subsequently added into 100mg catalyst sTiP-1-FluCpZrCl2, is passed through ethylene, by pressure
1.0MPa is increased and maintained, is reacted 1 hour at 60 DEG C；The activity for measuring catalyst is 600gPE/gcath.
Embodiment 15
A kind of spherical supported type metallocene catalyst is present embodiments provided, is carrier loaded bis- (tertiary fourths with embodiment 1
Cyclopentadienyl group) hafnium dichloride (tBuCp)2HfCl2It is obtained, specific preparation process are as follows:
It accurately weighs in the glass reactor that 5g sTiP-1 is transferred to after nitrogen is sufficiently displaced from, adds under nitrogen protection
Enter the toluene 25ml of water removal purification；After stirring makes it be uniformly dispersed, it is added 16ml methylaluminoxane (toluene solution of 1.5M), in
40 DEG C are stirred 1 hour, the carrier activated.
100mg (tBuCp) is accurately weighed under nitrogen protection2HfCl2It is transferred to the reaction of the glass after nitrogen is sufficiently displaced from
In device, the toluene 10ml of water removal purification is added.It stirs to dissolve；It is added 1ml methylaluminoxane (toluene solution of 1.5M), in
40 DEG C of stirrings 1h, (tBuCp) activated2HfCl2Solution.
Under nitrogen protection by (tBuCp) of activation2HfCl2Solution is added in the carrier of activation, stirs 2 hours in 40 DEG C；
After reaction, it stands, filters out liquid after layering, washed twice with the toluene of 20ml water removal purification, then removed water and refined with 30ml
Hexane wash twice.Solid is dried in vacuo, spherical supported type metallocene catalyst is obtained and (is denoted as sTiP-1- (tBuCp)2HfCl2)。
In 2L stainless steel polymerization autoclave, after being sufficiently displaced from ethylene, the hexane of 1L water removal purification is added, 2ml is added
Triethyl aluminum (hexane solution of 2.4M), is subsequently added into 100mg catalyst sTiP-1- (tBuCp)2HfCl2, it is passed through ethylene, will be pressed
Power increases and maintains 1.0MPa, reacts 1 hour at 60 DEG C；The activity for measuring catalyst is 2100gPE/gcath.
Embodiment 16
A kind of spherical supported type metallocene catalyst is present embodiments provided, is carrier loaded bis- (tertiary fourths with embodiment 1
Cyclopentadienyl group) di-methylation hafnium (BuCp)2Hf(CH3)2It is obtained, specific preparation process are as follows:
It accurately weighs in the glass reactor that 5g sTiP-1 is transferred to after nitrogen is sufficiently displaced from, adds under nitrogen protection
Enter the toluene 25ml of water removal purification；After stirring makes it be uniformly dispersed, it is added 15ml methylaluminoxane (toluene solution of 1.5M), in
40 DEG C are stirred 1 hour, the carrier activated.
100mg (BuCp) is accurately weighed under nitrogen protection2Hf(CH3)2The glass being transferred to after nitrogen is sufficiently displaced from is anti-
It answers in device, the toluene 10ml of water removal purification is added；It stirs to dissolve.It is added 1ml methylaluminoxane (toluene solution of 1.5M),
In 40 DEG C of stirrings 1h, (BuCp) activated2Hf(CH3)2Solution.
2 solution of (BuCp) 2Hf (CH3) of activation is added under nitrogen protection in the carrier of activation, it is small in 40 DEG C of stirrings 2
When；After reaction, it stands, filters out liquid after layering, washed twice with the toluene of 20ml water removal purification, then remove crystal with 30ml
The hexane of system washes twice；Solid is dried in vacuo, spherical supported type metallocene catalyst is obtained and (is denoted as sTiP-1- (BuCp)2Hf(CH3)2)。
In 2L stainless steel polymerization autoclave, after being sufficiently displaced from ethylene, the hexane of 1L water removal purification is added, 2ml is added
Triethyl aluminum (hexane solution of 2.4M), is subsequently added into 100mg catalyst sTiP-1- (BuCp)2Hf(CH3)2, it is passed through ethylene, it will
Pressure rise simultaneously maintains 1.0MPa, reacts 1 hour at 60 DEG C；The activity for measuring catalyst is 1810gPE/gcath.
Embodiment 17
A kind of spherical supported type metallocene catalyst is present embodiments provided, is the carrier loaded ring penta 2 with embodiment 6
Alkenyl titanium trichloride CpTiCl3It is obtained, specific preparation process are as follows:
It accurately weighs in the glass reactor that 5g sZrP is transferred to after nitrogen is sufficiently displaced from, is added under nitrogen protection
Remove water the toluene 25ml of purification；After stirring makes it be uniformly dispersed, it is added 20ml methylaluminoxane (toluene solution of 1.5M), in 40
DEG C stirring 1 hour, the carrier activated.
50mg CpTiCl is accurately weighed under nitrogen protection3It is transferred in the glass reactor after nitrogen is sufficiently displaced from,
The toluene 10ml of water removal purification is added.It stirs to dissolve；It is added 1ml methylaluminoxane (toluene solution of 1.5M), in 40 DEG C
Stir 1h, the CpTiCl activated3Solution.
Under nitrogen protection by the CpTiCl of activation3Solution is added in the carrier of activation, stirs 2 hours in 40 DEG C；Reaction
After, it stands, filters out liquid after layering, washed twice with the toluene of 20ml water removal purification, then remove water oneself of purification with 30ml
Alkane washes twice.Solid is dried in vacuo, spherical supported type metallocene catalyst is obtained and (is denoted as sZrP-CpTiCl3)。
In 2L stainless steel polymerization autoclave, after being sufficiently displaced from ethylene, the hexane of 1L water removal purification is added, 2ml is added
Triethyl aluminum (hexane solution of 2.4M), is subsequently added into 100mg catalyst sZrP-CpTiCl3, it is passed through ethylene, by pressure rise
And 1.0MPa is maintained, it is reacted 1 hour at 60 DEG C；The activity for measuring catalyst is 80gPE/gcath.
Embodiment 18
A kind of spherical supported type metallocene catalyst is present embodiments provided, is the carrier loaded indenyl three with embodiment 6
Titanium chloride IndTiCl3It is obtained, specific preparation process are as follows:
It accurately weighs in the glass reactor that 5g sZrP is transferred to after nitrogen is sufficiently displaced from, is added under nitrogen protection
Remove water the toluene 25ml of purification；After stirring makes it be uniformly dispersed, it is added 20ml methylaluminoxane (toluene solution of 1.5M), in 40
DEG C stirring 1 hour, the carrier activated.
50mg IndTiCl is accurately weighed under nitrogen protection3The glass reactor being transferred to after nitrogen is sufficiently displaced from
In, the toluene 10ml of water removal purification is added；It stirs to dissolve, is added 1ml methylaluminoxane (toluene solution of 1.5M), in 40
DEG C stirring 1h, the IndTiCl activated3Solution.
Under nitrogen protection by the IndTiCl of activation3Solution is added in the carrier of activation, stirs 2 hours in 40 DEG C；Reaction
After, it stands, filters out liquid after layering, washed twice with the toluene of 20ml water removal purification, then remove water oneself of purification with 30ml
Alkane washes twice；Solid is dried in vacuo, spherical supported type metallocene catalyst is obtained and (is denoted as sZrP-IndTiCl3)。
In 2L stainless steel polymerization autoclave, after being sufficiently displaced from ethylene, the hexane of 1L water removal purification is added, 2ml is added
Triethyl aluminum (hexane solution of 2.4M), is subsequently added into 100mg catalyst sZrP-IndTiCl3, it is passed through ethylene, by pressure rise
And 1.0MPa is maintained, it is reacted 1 hour at 60 DEG C；The activity for measuring catalyst is 100gPE/gcath.
Embodiment 19
A kind of spherical supported type metallocene catalyst is present embodiments provided, is the carrier loaded pentamethyl with embodiment 6
Cyclopentadienyl group titanium trichloride Cp*TiCl3It is obtained, specific preparation process are as follows:
It accurately weighs in the glass reactor that 5g sZrP is transferred to after nitrogen is sufficiently displaced from, is added under nitrogen protection
Remove water the toluene 25ml of purification；After stirring makes it be uniformly dispersed, it is added 20ml methylaluminoxane (toluene solution of 1.5M), in 40
DEG C stirring 1 hour, the carrier activated.
50mg Cp*TiCl is accurately weighed under nitrogen protection3The glass reactor being transferred to after nitrogen is sufficiently displaced from
In, the toluene 10ml of water removal purification is added；It stirs to dissolve, is added 1ml methylaluminoxane (toluene solution of 1.5M), in 40
DEG C stirring 1h, the Cp*TiCl activated3Solution.
Under nitrogen protection by the Cp*TiCl of activation3Solution is added in the carrier of activation, stirs 2 hours in 40 DEG C；Reaction
After, it stands, filters out liquid after layering, washed twice with the toluene of 20ml water removal purification, then remove water oneself of purification with 30ml
Alkane washes twice；Solid is dried in vacuo, spherical supported type metallocene catalyst is obtained and (is denoted as sZrP-Cp*TiCl3)。
In 2L stainless steel polymerization autoclave, after being sufficiently displaced from ethylene, the hexane of 1L water removal purification is added, 2ml is added
Triethyl aluminum (hexane solution of 2.4M), is subsequently added into 100mg catalyst sZrP-Cp*TiCl3, it is passed through ethylene, by pressure rise
And 1.0MPa is maintained, it is reacted 1 hour at 60 DEG C；The activity for measuring catalyst is 110gPE/gcath.
Embodiment 20
A kind of spherical supported type metallocene catalyst is present embodiments provided, is the carrier loaded pentamethyl with embodiment 1
Cyclopentadienyl group tri-chlorination zirconium Cp*ZrCl3It is obtained, specific preparation process are as follows:
It accurately weighs in the glass reactor that 5g sTiP-1 is transferred to after nitrogen is sufficiently displaced from, adds under nitrogen protection
Enter the toluene 25ml of water removal purification；After stirring makes it be uniformly dispersed, it is added 20ml methylaluminoxane (toluene solution of 1.5M), in
40 DEG C are stirred 1 hour, the carrier activated.
50mg Cp*ZrCl is accurately weighed under nitrogen protection3The glass reactor being transferred to after nitrogen is sufficiently displaced from
In, the toluene 10ml of water removal purification is added；It stirs to dissolve.It is added 1ml methylaluminoxane (toluene solution of 1.5M), in 40
DEG C stirring 1h, the Cp*ZrCl activated3Solution.
Under nitrogen protection by the Cp*ZrCl of activation3Solution is added in the carrier of activation, stirs 2 hours in 40 DEG C；Reaction
After, it stands, filters out liquid after layering, washed twice with the toluene of 20ml water removal purification, then remove water oneself of purification with 30ml
Alkane washes twice；Solid is dried in vacuo, spherical supported type metallocene catalyst is obtained and (is denoted as sTiP-1-Cp*ZrCl3)。
In 2L stainless steel polymerization autoclave, after being sufficiently displaced from ethylene, the hexane of 1L water removal purification is added, 2ml is added
Triethyl aluminum (hexane solution of 2.4M), is subsequently added into 100mg catalyst sTiP-1-Cp*ZrCl3, it is passed through ethylene, by pressure liter
Height simultaneously maintains 1.0MPa, reacts 1 hour at 60 DEG C；The activity for measuring catalyst is 100gPE/gcath.
Embodiment 21
A kind of spherical supported type metallocene catalyst is present embodiments provided, is the carrier loaded dimethyl with embodiment 1
Bis- (penta bicycloenyl of ring) silicon substrate zirconium dichloride Me2SiCp2ZrCl2It is obtained, specific preparation process are as follows:
It accurately weighs in the glass reactor that 5g sTiP-1 is transferred to after nitrogen is sufficiently displaced from, adds under nitrogen protection
Enter the toluene 25ml of water removal purification.After stirring makes it be uniformly dispersed, it is added 16ml methylaluminoxane (toluene solution of 1.5M), in
40 DEG C are stirred 1 hour, the carrier activated.
50mg Me is accurately weighed under nitrogen protection2SiCp2ZrCl2It is transferred to the reaction of the glass after nitrogen is sufficiently displaced from
In device, the toluene 10ml of water removal purification is added；It stirs to dissolve.It is added 1ml methylaluminoxane (toluene solution of 1.5M), in
40 DEG C of stirrings 1h, the Me activated2SiCp2ZrCl2Solution.
Under nitrogen protection by the Me of activation2SiCp2ZrCl2Solution is added in the carrier of activation, stirs 2 hours in 40 DEG C；
After reaction, it stands, filters out liquid after layering, washed twice with the toluene of 20ml water removal purification, then removed water and refined with 30ml
Hexane wash twice；Solid is dried in vacuo, spherical supported type metallocene catalyst is obtained and (is denoted as sTiP-1-
Me2SiCp2ZrCl2)。
In 2L stainless steel polymerization autoclave, after being sufficiently displaced from ethylene, the hexane of 1L water removal purification is added, 2ml is added
Triethyl aluminum (hexane solution of 2.4M), is subsequently added into 100mg catalyst sTiP-1-Me2SiCp2ZrCl2, it is passed through ethylene, will be pressed
Power increases and maintains 1.0MPa, reacts 1 hour at 60 DEG C；The activity for measuring catalyst is 450gPE/gcath.
Embodiment 22
A kind of spherical supported type metallocene catalyst is present embodiments provided, is the carrier loaded dimethyl with embodiment 1
Bis- (9- fluorenyl) silicon substrate zirconium dichloride Me2Si(9-Flu)2ZrCl2It is obtained, specific preparation process are as follows:
It accurately weighs in the glass reactor that 5g sTiP-1 is transferred to after nitrogen is sufficiently displaced from, adds under nitrogen protection
Enter the toluene 25ml of water removal purification；After stirring makes it be uniformly dispersed, it is added 16ml methylaluminoxane (toluene solution of 1.5M), in
40 DEG C are stirred 1 hour, the carrier activated.
100mg Me is accurately weighed under nitrogen protection2Si(9-Flu)2ZrCl2The glass being transferred to after nitrogen is sufficiently displaced from
In glass reactor, the toluene 10ml of water removal purification is added；It stirs to dissolve, 5ml methylaluminoxane is added, and (toluene of 1.5M is molten
Liquid), in 40 DEG C of stirrings 1h, the Me activated2Si(9-Flu)2ZrCl2Solution.
Under nitrogen protection by the Me of activation2Si(9-Flu)2ZrCl2Solution is added in the carrier of activation, stirs 2 in 40 DEG C
Hour；After reaction, it stands, filters out liquid after layering, washed twice with the toluene of 20ml water removal purification, then removed water with 30ml
The hexane of purification washes twice；Solid is dried in vacuo, spherical supported type metallocene catalyst is obtained and (is denoted as sTiP-1-Me2Si
(9-Flu)2ZrCl2)。
In 2L stainless steel polymerization autoclave, after being sufficiently displaced from ethylene, the hexane of 1L water removal purification is added, 2ml is added
Triethyl aluminum (hexane solution of 2.4M), is subsequently added into 100mg catalyst sTiP-1-Me2Si(9-Flu)2ZrCl2, it is passed through second
Alkene by pressure rise and maintains 1.0MPa, reacts 1 hour at 60 DEG C；The activity for measuring catalyst is 340gPE/gcath.
Embodiment 23
A kind of spherical supported type metallocene catalyst is present embodiments provided, is sub- with the carrier loaded isopropyl of embodiment 1
Bis- (9- fluorenyl) the zirconium dichloride iPr (9-Flu) of base2ZrCl2It is obtained, specific preparation process are as follows:
It accurately weighs in the glass reactor that 5g sTiP-1 is transferred to after nitrogen is sufficiently displaced from, adds under nitrogen protection
Enter the toluene 25ml of water removal purification；After stirring makes it be uniformly dispersed, it is added 16ml methylaluminoxane (toluene solution of 1.5M), in
40 DEG C are stirred 1 hour, the carrier activated.
100mg iPr (9-Flu) is accurately weighed under nitrogen protection2ZrCl2The glass being transferred to after nitrogen is sufficiently displaced from
In reactor, the toluene 10ml of water removal purification is added；It stirs to dissolve.5ml methylaluminoxane is added, and (toluene of 1.5M is molten
Liquid), in 40 DEG C of stirring 1h, the iPr activated (9-Flu) 2ZrCl2 solution.
Under nitrogen protection by the iPr of activation (9-Flu)2ZrCl2Solution is added in the carrier of activation, small in 40 DEG C of stirrings 2
When；After reaction, it stands, filters out liquid after layering, washed twice with the toluene of 20ml water removal purification, then remove crystal with 30ml
The hexane of system washes twice；Solid is dried in vacuo, spherical supported type metallocene catalyst is obtained and (is denoted as sTiP-1-iPr (9-
Flu)2ZrCl2)。
In 5L stainless steel polymerization autoclave, after being sufficiently displaced from nitrogen, 1kg liquid propene is added, 1ml triethyl group is added
Aluminium (hexane solution of 2.4M), is subsequently added into 100mg catalyst sTiP-1-iPr (9-Flu)2ZrCl2, increase temperature to 60 DEG C it is anti-
It answers 2 hours；The activity for measuring catalyst is 210gPP/gcath.
Embodiment 24
A kind of spherical supported type metallocene catalyst is present embodiments provided, is sub- with the carrier loaded isopropyl of embodiment 1
Cyclopentadienyl group (9- fluorenyl) zirconium dichloride iPrCp (9-Flu) ZrCl2It is obtained, specific preparation process are as follows:
It accurately weighs in the glass reactor that 5g sTiP-1 is transferred to after nitrogen is sufficiently displaced from, adds under nitrogen protection
Enter the toluene 25ml of water removal purification；After stirring makes it be uniformly dispersed, it is added 16ml methylaluminoxane (toluene solution of 1.5M), in
40 DEG C are stirred 1 hour, the carrier activated.
100mg iPrCp (9-Flu) ZrCl is accurately weighed under nitrogen protection2The glass being transferred to after nitrogen is sufficiently displaced from
In glass reactor, the toluene 10ml of water removal purification is added；It stirs to dissolve.5ml methylaluminoxane is added, and (toluene of 1.5M is molten
Liquid), in 40 DEG C of stirring 1h, the iPrCp activated (9-Flu) ZrCl2Solution.
Under nitrogen protection by the iPrCp of activation (9-Flu) ZrCl2Solution is added in the carrier of activation, stirs 2 in 40 DEG C
Hour；After reaction, it stands, filters out liquid after layering, washed twice with the toluene of 20ml water removal purification, then removed water with 30ml
The hexane of purification washes twice；Solid is dried in vacuo, spherical supported type metallocene catalyst is obtained and (is denoted as sTiP-1-iPrCp
(9-Flu)ZrCl2)。
In 5L stainless steel polymerization autoclave, after being sufficiently displaced from nitrogen, 1kg liquid propene is added, 1ml triethyl group is added
Aluminium (hexane solution of 2.4M) is subsequently added into 100mg catalyst sTiP-1-iPrCp (9-Flu) ZrCl2, temperature is increased to 60 DEG C
Reaction 2 hours；The activity for measuring catalyst is 200gPP/gcath.
Embodiment 25
A kind of spherical supported type metallocene catalyst is present embodiments provided, is sub- with the carrier loaded hexichol of embodiment 1
Methyl cyclopentadienyl (9- fluorenyl) zirconium dichloride Ph2CCp(9-Flu)ZrCl2It is obtained, specific preparation process are as follows:
It accurately weighs in the glass reactor that 5g sTiP-1 is transferred to after nitrogen is sufficiently displaced from, adds under nitrogen protection
Enter the toluene 25ml of water removal purification；After stirring makes it be uniformly dispersed, it is added 16ml methylaluminoxane (toluene solution of 1.5M), in
40 DEG C are stirred 1 hour, the carrier activated.
100mg Ph is accurately weighed under nitrogen protection2CCp(9-Flu)ZrCl2The glass being transferred to after nitrogen is sufficiently displaced from
In glass reactor, the toluene 10ml of water removal purification is added.It stirs to dissolve；5ml methylaluminoxane is added, and (toluene of 1.5M is molten
Liquid), in 40 DEG C of stirrings 1h, the Ph activated2CCp(9-Flu)ZrCl2Solution.
Under nitrogen protection by the Ph of activation2CCp(9-Flu)ZrCl2Solution is added in the carrier of activation, stirs 2 in 40 DEG C
Hour；After reaction, it stands, filters out liquid after layering, washed twice with the toluene of 20ml water removal purification, then removed water with 30ml
The hexane of purification washes twice.Solid is dried in vacuo, spherical supported type metallocene catalyst is obtained and (is denoted as sTiP-1-
Ph2CCp(9-Flu)ZrCl2)。
In 5L stainless steel polymerization autoclave, after being sufficiently displaced from nitrogen, 1kg liquid propene is added, 1ml triethyl group is added
Aluminium (hexane solution of 2.4M), is subsequently added into 100mg catalyst sTiP-1-Ph2CCp(9-Flu)ZrCl2, temperature is increased to 60 DEG C
Reaction 2 hours；The activity for measuring catalyst is 250gPP/gcath.
Embodiment 26
A kind of spherical supported type metallocene catalyst is present embodiments provided, is the carrier loaded rac- second with embodiment 1
The double tetrahydroindenyl zirconium dichloride rac-EtInd of alkenyl2ZrCl2It is obtained, specific preparation process are as follows:
It accurately weighs in the glass reactor that 5g sTiP-1 is transferred to after nitrogen is sufficiently displaced from, adds under nitrogen protection
Enter the toluene 25ml of water removal purification；After stirring makes it be uniformly dispersed, it is added 16ml methylaluminoxane (toluene solution of 1.5M), in
40 DEG C are stirred 1 hour, the carrier activated.
60mg rac-EtInd is accurately weighed under nitrogen protection2ZrCl2The glass being transferred to after nitrogen is sufficiently displaced from is anti-
It answers in device, the toluene 10ml of water removal purification is added；It stirs to dissolve, 10ml methylaluminoxane is added, and (toluene of 1.5M is molten
Liquid), in 40 DEG C of stirrings 1h, the rac-EtInd activated2ZrCl2Solution.
Under nitrogen protection by the rac-EtInd of activation2ZrCl2Solution is added in the carrier of activation, small in 40 DEG C of stirrings 2
When；After reaction, it stands, filters out liquid after layering, washed twice with the toluene of 20ml water removal purification, then remove crystal with 30ml
The hexane of system washes twice；Solid is dried in vacuo, spherical supported type metallocene catalyst is obtained and (is denoted as sTiP-1-rac-
EtInd2ZrCl2)。
In 5L stainless steel polymerization autoclave, after being sufficiently displaced from nitrogen, 1kg liquid propene is added, 1ml triethyl group is added
Aluminium (hexane solution of 2.4M), is subsequently added into 100mg catalyst sTiP-1-rac-EtInd2ZrCl2, increase temperature to 60 DEG C it is anti-
It answers 2 hours；The activity for measuring catalyst is 1500gPP/gcath.
Embodiment 27
A kind of spherical supported type metallocene catalyst is present embodiments provided, is the carrier loaded rac- second with embodiment 1
Bis- (tetrahydro indenyl) zirconium dichloride rac-Et (IndH of alkenyl4)2ZrCl2It is obtained, specific preparation process are as follows:
It accurately weighs in the glass reactor that 5g sTiP-1 is transferred to after nitrogen is sufficiently displaced from, adds under nitrogen protection
Enter the toluene 25ml of water removal purification；After stirring makes it be uniformly dispersed, it is added 16ml methylaluminoxane (toluene solution of 1.5M), in
40 DEG C are stirred 1 hour, the carrier activated.
100mg rac-Et (IndH is accurately weighed under nitrogen protection4)2ZrCl2It is transferred to after nitrogen is sufficiently displaced from
In glass reactor, the toluene 10ml of water removal purification is added；It stirs to dissolve, the 15ml methylaluminoxane (first of 1.5M is added
Benzole soln), in 40 DEG C of stirrings 1h, the rac-Et (IndH activated4)2ZrCl2Solution.
Under nitrogen protection by the rac-Et (IndH of activation4)2ZrCl2Solution is added in the carrier of activation, stirs in 40 DEG C
2 hours；After reaction, it stands, filters out liquid after layering, washed twice with the toluene of 20ml water removal purification, then removed with 30ml
The hexane of crystal washes twice；Solid is dried in vacuo, spherical supported type metallocene catalyst is obtained and (is denoted as sTiP-1-
rac-Et(IndH4)2ZrCl2)。
In 5L stainless steel polymerization autoclave, after being sufficiently displaced from nitrogen, 1kg liquid propene is added, 1ml triethyl group is added
Aluminium (hexane solution of 2.4M) is subsequently added into 100mg catalyst sTiP-1-rac-Et (IndH4)2ZrCl2, temperature is increased to 60
DEG C reaction 2 hours；The activity for measuring catalyst is 1830gPP/gcath.
Embodiment 28
A kind of spherical supported type metallocene catalyst is present embodiments provided, is the carrier loaded rac- bis- with embodiment 1
Bis- (2- methyl -4,5- benzo indenyl) the silicon substrate zirconium dichloride rac-Me of methyl2Si(2-Me-4,5-BenzInd)2ZrCl2It is made
, specific preparation process are as follows:
It accurately weighs in the glass reactor that 5g sTiP-1 is transferred to after nitrogen is sufficiently displaced from, adds under nitrogen protection
Enter the toluene 25ml of water removal purification；After stirring makes it be uniformly dispersed, it is added 15ml methylaluminoxane (toluene solution of 1.5M), in
40 DEG C are stirred 1 hour, the carrier activated.
100mg rac-Me is accurately weighed under nitrogen protection2Si(2-Me-4,5-BenzInd)2ZrCl2It is transferred to through nitrogen
Gas be sufficiently displaced from after glass reactor in, be added water removal purification toluene 20ml；After stirring to dissolve completely, 10ml is added
Methylaluminoxane (toluene solution of 1.5M) stirs 1 hour, the rac-Me activated in 40 DEG C2Si(2-Me-4,5-
BenzInd)2ZrCl2Solution.
Under nitrogen protection by the rac-Me of activation2Si(2-Me-4,5-BenzInd)2ZrCl2The load of activation is added in solution
In body, stirred 2 hours in 40 DEG C；After reaction, it stands, filters out liquid after layering, washed with the toluene of 20ml water removal purification
Twice, then with the hexane of 30ml water removal purification it washes twice；Solid is dried in vacuo, spherical supported type metallocene catalyst is obtained
(it is denoted as sTiP-1-rac-Me2Si(2-Me-4,5-BenzInd)2ZrCl2)。
In 5L stainless steel polymerization autoclave, after being sufficiently displaced from nitrogen, 1kg liquid propene is added, 1ml triethyl group is added
Aluminium (hexane solution of 2.4M), is subsequently added into 100mg catalyst sTiP-1-rac-Me2Si(2-Me-4,5-BenzInd)2ZrCl2, temperature is increased to 60 DEG C of reactions, 2 hours (obtained polyacrylic scanning electron microscope (SEM) photograph is as shown in Figure 4)；Measure catalyst
Activity is 2130gPP/gcath.
In 5L stainless steel polymerization autoclave, after being sufficiently displaced from nitrogen, 1kg liquid propene is added, 1ml triethyl group is added
Aluminium (hexane solution of 2.4M), is subsequently added into 100mg catalyst sTiP-1-rac-Me2Si(2-Me-4,5-BenzInd)2ZrCl2, increase temperature to 60 DEG C react 30 minutes, obtained polypropylene 50g；Fig. 5 is that (polymerization is anti-for polyacrylic transmission electron microscope picture
It should only be reacted 30 minutes at 60 DEG C, the relative amount of carrier in polymer can be made higher in this way, convenient for being carried in observation polymer
The distribution situation of body), the scale in figure is 6nm, and the black portions in figure are carrier, by the figure it is found that carrier is in polymer
It is middle evenly dispersed at nanoscale.
Embodiment 29
A kind of spherical supported type metallocene catalyst is present embodiments provided, is the carrier loaded rac- bis- with embodiment 1
Bis- (2- methyl 4-phenyl indenyl) the silicon substrate zirconium dichloride rac-Me of methyl2Si(2-Me-4-PhInd)2ZrCl2It is obtained, specifically
Preparation process are as follows:
It accurately weighs in the glass reactor that 5g sTiP-1 is transferred to after nitrogen is sufficiently displaced from, adds under nitrogen protection
Enter the toluene 25ml of water removal purification；After stirring makes it be uniformly dispersed, it is added 16ml methylaluminoxane (toluene solution of 1.5M), in
40 DEG C are stirred 2 hours, the carrier activated.
100mg rac-Me is accurately weighed under nitrogen protection2Si(2-Me-4-PhInd)2ZrCl2It is transferred to and is filled through nitrogen
It splits in the glass reactor after changing, the toluene 50ml of water removal purification is added；After stirring to dissolve completely, 10ml methyl is added
Aikyiaiurnirsoxan beta (toluene solution of 1.5M) stirs 1 hour, the rac-Me activated in 40 DEG C2Si(2-Me-4-PhInd)2ZrCl2
Solution.
Under nitrogen protection by the rac-Me of activation2Si(2-Me-4-PhInd)2ZrCl2Solution is added in the carrier of activation,
It is stirred 2 hours in 40 DEG C；After reaction, it stands, filters out liquid after layering, washed twice with the toluene of 20ml water removal purification,
It is washed twice again with the hexane of 30ml water removal purification；Solid is dried in vacuo, spherical supported type metallocene catalyst is obtained and (is denoted as
sTiP-1-rac-Me2Si(2-Me-4-PhInd)2ZrCl2)。
In 5L stainless steel polymerization autoclave, after being sufficiently displaced from nitrogen, 1kg liquid propene is added, 1ml triethyl group is added
Aluminium (hexane solution of 2.4M) is subsequently added into 100mg catalysis sTiP-1-rac-Me2Si(2-Me-4-PhInd)2ZrCl2, increase
Temperature to 60 DEG C react 2 hours；The activity for measuring catalyst is 2400gPP/gcath.
Embodiment 30
A kind of spherical supported type metallocene catalyst is present embodiments provided, is the carrier loaded [Me with embodiment 62Si
(Me4Cp)(NtBu)]TiCl2 It is obtained, specific preparation process are as follows:
It accurately weighs in the glass reactor that 5g sZrP is transferred to after nitrogen is sufficiently displaced from, is added under nitrogen protection
Remove water the toluene 25ml of purification；After stirring makes it be uniformly dispersed, it is added 16ml methylaluminoxane (toluene solution of 1.5M), in 40
DEG C stirring 2 hours, the carrier activated.
100mg [Me is accurately weighed under nitrogen protection2Si(Me4Cp)(NtBu)]TiCl2It is transferred to and is sufficiently displaced from through nitrogen
In glass reactor afterwards, the toluene 50ml of water removal purification is added；After stirring to dissolve completely, 2ml methylaluminoxane is added
(toluene solution of 1.5M) stirs 1 hour, [the Me activated in 40 DEG C2Si(Me4Cp)(NtBu)]TiCl2Solution.
Under nitrogen protection by the [Me of activation2Si(Me4Cp)(NtBu)]TiCl2Solution is added in the carrier of activation, in 40
DEG C stirring 2 hours；After reaction, it stands, filters out liquid after layering, washed twice with the toluene of 20ml water removal purification, then use
The hexane of 30ml water removal purification washes twice；Solid is dried in vacuo, spherical supported type metallocene catalyst is obtained and (is denoted as
sZrP-[Me2Si(Me4Cp)(NtBu)]TiCl2)。
In 2L stainless steel polymerization autoclave, after being sufficiently displaced from ethylene, the hexane of 1L water removal purification is added, 2ml is added
Triethyl aluminum (hexane solution of 2.4M) is subsequently added into 100mg catalyst sZrP- [Me2Si(Me4Cp)(NtBu)]TiCl2, lead to
Enter ethylene, by pressure rise and maintain 1.0MPa, is reacted 1 hour at 60 DEG C；The activity for measuring catalyst is 2300gPE/
gcat·h。
Claims (16)
1. a kind of spherical supported type metallocene catalyst, wherein the carrier of the catalyst is spherical phosphoric acid hydrogen titanium/zirconium class chemical combination
Object, the major catalyst of the catalyst are metallocene compound, and the co-catalyst of the catalyst is methylaluminoxane；
Described spherical shape phosphoric acid hydrogen titanium/Zirconium compound include one of phosphoric acid hydrogen titanium, modified phosphate hydrogen titanium and phosphoric acid hydrogen zirconium or
Several combinations；
The content of the central metal of the metallocene compound in the catalyst is 0.1wt%-0.4wt%, the catalysis
Aluminium content in agent is 5wt%-20wt%；
The modified phosphate hydrogen titanium includes organic modified phosphate hydrogen titanium or acidified modified phosphoric acid hydrogen titanium；
Wherein, the organically-modified phosphoric acid hydrogen titanium includes benzenephosphonic acid titanium and phenyl-phosphonic acid-phosphoric acid hydrogen titanium, the phenyl-phosphonic acid-phosphoric acid hydrogen
The chemical formula of titanium is Ti (C6H5PO3)x(HPO4)2-x, 0 < x < 2.
2. spherical supported type metallocene catalyst according to claim 1, wherein 0.5≤x≤1.5.
3. spherical supported type metallocene catalyst according to claim 1, wherein the center gold of the metallocene compound
Belonging to is Group IVB transition metal.
4. spherical supported type metallocene catalyst according to claim 3, wherein the central metal is titanium, zirconium or hafnium.
5. spherical supported type metallocene catalyst according to claim 3, wherein the metallocene compound includes non-bridge
Even dis-cyclopentadiene compounds, non-bridged Monodentate compound, the metallocene compound containing bridging and constrained geometry metallocene chemical combination
The combination of one or more of object.
6. spherical supported type metallocene catalyst according to claim 5, wherein the non-bridged dis-cyclopentadiene compounds packet
Include: bis cyclopentadienyl zirconium dichloride, two indenyl zirconium of dichloro, bis- (butyl cyclopentadienyl group) zirconium dichlorides, fluorenyl cyclopentadiene base zirconium dichloride,
Dichloro hafnocene, bis- (butyl cyclopentadienyl group) hafnium dichlorides or bis- (butyl cyclopentadienyl group) di-methylation hafniums.
7. spherical supported type metallocene catalyst according to claim 5, wherein the non-bridged Monodentate compound packet
It includes: cyclopentadienyl group titanium trichloride, indenyl titanium trichloride, pentamethylcyclopentadiene base titanium trichloride or pentamethylcyclopentadiene base
Tri-chlorination zirconium.
8. spherical supported type metallocene catalyst according to claim 5, wherein the metallocene chemical combination containing bridging
Object includes: bis- (cyclopentadienyl group) the silicon substrate zirconium dichlorides of dimethyl, bis- (9- fluorenyl) the silicon substrate zirconium dichlorides of dimethyl, isopropyl subunit
Bis- (9- fluorenyl) zirconium dichlorides, isopropyl subunit cyclopentadienyl group (9- fluorenyl) zirconium dichloride, diphenyl methylene cyclopentadienyl group (9-
Fluorenyl) zirconium dichloride, rac- vinyl double tetrahydroindenyl zirconium dichlorides, bis- (tetrahydro indenyl) zirconium dichlorides of rac- vinyl, rac- bis-
Bis- (2- methyl -4,5- benzo indenyl) the silicon substrate zirconium dichlorides of methyl or bis- (the 2- methyl 4-phenyl indenyl) silicon substrates of rac- dimethyl
Zirconium dichloride.
9. spherical supported type metallocene catalyst according to claim 5, wherein the constrained geometry metallocene
Closing object includes [Me2Si(Me4Cp)(NtBu)]TiCl2。
10. a kind of preparation method of spherical supported type metallocene catalyst described in any one of claim 1-9, this method packet
Include following steps:
By spherical phosphoric acid hydrogen titanium/Zirconium compound support dispersion in toluene, methylaluminoxane is added at 20 DEG C -50 DEG C, stirs
It mixes 20 minutes to 2 hours, the spherical phosphoric acid hydrogen titanium/Zirconium compound carrier activated；The mole of methylaluminoxane is with aluminium
The amount ratio of meter, methylaluminoxane and ball type carrier is 3-9mmol/g；
Metallocene compound is dissolved in toluene, methylaluminoxane is added at 20 DEG C -50 DEG C, stirs 20 minutes to 2 hours,
The metallocene compound solution activated；The mass ratio of the metallocene compound and ball type carrier is 0.01-0.03:1；First
For the mole of base aikyiaiurnirsoxan beta in terms of aluminium, the amount ratio of methylaluminoxane and metallocene compound is 0.015-0.3mol/g；
Spherical phosphoric acid hydrogen titanium/Zirconium compound carrier of above-mentioned activation is mixed with the metallocene compound solution of activation, then
Agitated processing obtains mixed system, and mixed system is washed, solid sediment is obtained by filtration, and solid sediment is through being dried to obtain
Spherical supported type metallocene catalyst.
11. the preparation method of spherical supported type metallocene catalyst according to claim 10, wherein
The condition of the stir process are as follows: at 20 DEG C -50 DEG C, stir 30 minutes to 3 hours.
12. the application of spherical supported type metallocene catalyst described in any one of claim 1-9 in olefin polymerization.
13. one kind is made by spherical supported type metallocene catalyst catalysis in olefine polymerization described in any one of claim 1-9
Polyolefin-nanocomposite, wherein in the polyolefin-nanocomposite, phosphoric acid hydrogen titanium/Zirconium compound with
Nanoscale disperses in a polymer matrix.
14. a kind of ball type carrier for spherical supported type metallocene catalyst described in any one of claim 1-9,
In,
The shape of the ball type carrier is microspheroidal, and average grain diameter is 5-50 μm, specific surface 100-400m2/ g, specific pore volume are
0.8-1.6cc/g；
Wherein, the ball type carrier is phenyl-phosphonic acid-phosphoric acid hydrogen titanium, and chemical formula is Ti (C6H5PO3)x(HPO4)2-x, 0 < x < 2.
15. ball type carrier according to claim 14, wherein 0.5≤x≤1.5.
16. a kind of preparation method of ball type carrier described in claim 14, wherein method includes the following steps:
Phosphoric acid hydrogen titanium/Zirconium compound and water are matched into resulting mixture, phosphoric acid hydrogen titanium/Zirconium compound and water quality in mixture
Than for 0.05-0.2:1；
The mixture is emulsified, phosphoric acid hydrogen titanium/Zirconium compound slurries are obtained；
The phosphoric acid hydrogen titanium/Zirconium compound slurries are spray-dried, spherical phosphoric acid hydrogen titanium/Zirconium compound is obtained
Grain；
The spherical phosphoric acid hydrogen titanium/Zirconium compound particle is subjected to vacuum dehydration processing at 100 DEG C -200 DEG C, then
It is cooled to room temperature under inert atmosphere protection, obtains ball type carrier.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510627473.9A CN106554433B (en) | 2015-09-28 | 2015-09-28 | Spherical load type metallocene catalyst |
| PCT/CN2016/074130 WO2017054398A1 (en) | 2015-09-28 | 2016-02-19 | Spherical supported transition metal catalyst |
| US15/747,268 US10808052B2 (en) | 2015-09-28 | 2016-02-19 | Spherical supported transition metal catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510627473.9A CN106554433B (en) | 2015-09-28 | 2015-09-28 | Spherical load type metallocene catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106554433A CN106554433A (en) | 2017-04-05 |
| CN106554433B true CN106554433B (en) | 2019-06-11 |
Family
ID=58416544
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510627473.9A Active CN106554433B (en) | 2015-09-28 | 2015-09-28 | Spherical load type metallocene catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106554433B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110479377B (en) * | 2019-08-06 | 2021-11-16 | 南方医科大学 | Catalyst for reaction of 4-iodonitrobenzene and phenylacetylene |
| CN114011469B (en) * | 2021-11-26 | 2023-11-21 | 中化泉州石化有限公司 | Catalyst composition for ethylene oligomerization |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995023816A1 (en) * | 1994-03-01 | 1995-09-08 | Mobil Oil Corpporation | Olefin polymerization catalysts |
| CN1182095A (en) * | 1996-10-31 | 1998-05-20 | 三菱化学株式会社 | Ethylene-alpha-olefin copolymer |
| CN101580561A (en) * | 2009-05-27 | 2009-11-18 | 中国石油天然气股份有限公司 | Supported polyolefin catalyst, preparation and application |
-
2015
- 2015-09-28 CN CN201510627473.9A patent/CN106554433B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995023816A1 (en) * | 1994-03-01 | 1995-09-08 | Mobil Oil Corpporation | Olefin polymerization catalysts |
| CN1182095A (en) * | 1996-10-31 | 1998-05-20 | 三菱化学株式会社 | Ethylene-alpha-olefin copolymer |
| CN101580561A (en) * | 2009-05-27 | 2009-11-18 | 中国石油天然气股份有限公司 | Supported polyolefin catalyst, preparation and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106554433A (en) | 2017-04-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Resconi et al. | Diastereoselective Synthesis, molecular structure, and solution dynamics of meso-and rac-[ethylenebis (4, 7-dimethyl-η5-1-indenyl)] zirconium dichloride isomers and chain transfer reactions in propene polymerization with the rac isomer | |
| KR101618753B1 (en) | Solid particulate catalysts comprising bridged metallocenes | |
| AU2002366265B2 (en) | Production of olefin polymerisation catalysts | |
| KR101626069B1 (en) | Solid particulate catalysts comprising bridged metallocenes | |
| JP4837879B2 (en) | Polymerization method with mixed catalyst composition | |
| JP5956595B2 (en) | Non-supported heterogeneous polyolefin polymerization catalyst composition and process for producing the same | |
| CN1958621B (en) | Solid catalyst components in use for polymerizing olefin, catalyst, and application of catalyst | |
| CN103946245B (en) | Olefinic polymerization and copolymerization catalysts and the olefinic polymerization using it or process for copolymerization | |
| CN101045760B (en) | Metal composite catalyst for alkene polymerization and preparation method thereof | |
| JPH09506391A (en) | (Co) polymerization of olefins | |
| CN102336846B (en) | Loaded alpha-palladium diimine and method for preparing hyperbranched polyethylene by catalyzing with same | |
| CN102665909B (en) | Supported hybrid metallocene catalyst comprising three compounds, and method for preparing same | |
| CN101434666B (en) | Magnesium chloride/mesoporous molecular sieve bisupported Ziegler-Natta polyethylene catalyst, preparation and use | |
| CN101580561A (en) | Supported polyolefin catalyst, preparation and application | |
| JP6870121B2 (en) | Manufacturing method of heterophase propylene copolymer | |
| KR100270383B1 (en) | Olefin polymerization catalyst system | |
| CN106554433B (en) | Spherical load type metallocene catalyst | |
| CN103788252A (en) | Catalyst solid ingredient, catalyst containing catalyst solid ingredient and use of catalyst in olefin polymerization | |
| CN106905452A (en) | Alpha-olefin polymerization catalyst and preparation method and application | |
| CN103073661A (en) | Magnesium dichloride-based adducts and catalyst components obtained therefrom | |
| CN100400554C (en) | Catalyst components for propylene polymerization and catalyst thereof | |
| WO1999005153A1 (en) | Method for producing metallocenes | |
| CN104558286A (en) | Catalyst component for olefin polymerization and catalyst | |
| CN106554436B (en) | Spherical load type non-metallocene transition metal catalyst | |
| JP3907270B2 (en) | Method for producing C2-C12 alkene polymer with addition of reaction retarder |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220114 Address after: 100007 No. 9 North Main Street, Dongcheng District, Beijing, Dongzhimen Patentee after: PetroChina Company Limited Patentee after: Sinopec Research Institute of Petrochemical Co.,Ltd. Address before: 100007 No. 9 North Main Street, Dongcheng District, Beijing, Dongzhimen Patentee before: PetroChina Company Limited |
|
| TR01 | Transfer of patent right |